CN1129565C - 羰基化合物的氢化方法 - Google Patents
羰基化合物的氢化方法 Download PDFInfo
- Publication number
- CN1129565C CN1129565C CN98807361A CN98807361A CN1129565C CN 1129565 C CN1129565 C CN 1129565C CN 98807361 A CN98807361 A CN 98807361A CN 98807361 A CN98807361 A CN 98807361A CN 1129565 C CN1129565 C CN 1129565C
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- China
- Prior art keywords
- acid
- aldehyde
- carbonyl compound
- gram
- hydrogenation
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 57
- 150000001728 carbonyl compounds Chemical class 0.000 title claims abstract description 24
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims description 37
- -1 aliphatic aldehyde Chemical class 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 18
- 150000001299 aldehydes Chemical class 0.000 claims description 13
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 9
- 241000209094 Oryza Species 0.000 claims description 7
- 235000007164 Oryza sativa Nutrition 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 239000010931 gold Substances 0.000 claims description 7
- 235000009566 rice Nutrition 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 3
- MCXYTDHHOJAPGI-UHFFFAOYSA-N 2-(dihydroxymethyl)butanal Chemical compound CCC(C=O)C(O)O MCXYTDHHOJAPGI-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229910000838 Al alloy Inorganic materials 0.000 description 9
- 229910000881 Cu alloy Inorganic materials 0.000 description 9
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000004913 activation Effects 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- FTZILAQGHINQQR-UHFFFAOYSA-N 2-Methylpentanal Chemical compound CCCC(C)C=O FTZILAQGHINQQR-UHFFFAOYSA-N 0.000 description 4
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- YYKMQUOJKCKTSD-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanal Chemical compound CCC(CO)(CO)C=O YYKMQUOJKCKTSD-UHFFFAOYSA-N 0.000 description 2
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- BYGQBDHUGHBGMD-UHFFFAOYSA-N 2-methylbutanal Chemical compound CCC(C)C=O BYGQBDHUGHBGMD-UHFFFAOYSA-N 0.000 description 2
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- KSMVZQYAVGTKIV-UHFFFAOYSA-N decanal Chemical compound CCCCCCCCCC=O KSMVZQYAVGTKIV-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
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- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
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- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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Abstract
在块金形式拉尼铜催化剂的存在下，催化氢化羰基化合物或两种或多种羰基化合物的混合物。
Description
本发明涉及一种在拉尼(Raney)铜催化剂的存在下，催化氢化羰基化合物的方法。
羰基化合物的催化氢化，如将醛氢化来制备简单的官能化醇，在基础化学工业的生产中占据着重要地位。尤其是氢化通过羰基合成或醛醇反应所得到的醛。
很早就已知在悬浮或固定床工艺中催化氢化醛。工业体系几乎无一例外地使用固定床反应器进行操作。
特别使用的固定床催化剂是载体上的催化剂，如承载在SiO2或Al2O3上的Cu/Ni或Cu/Cr催化剂。
替代载体催化剂的合适催化剂为拉尼型催化剂。拉尼催化剂由于金属的表面积大而具有特别高的氢化活性。合适的金属为镍、钴、铁和铜。
SU430876描述在悬浮工艺中，于拉尼铜催化剂上氢化糠醛。悬浮法相对固定床法的缺点在于其催化剂消耗较大。此外，需要在另一步骤中将该催化剂从反应混合物中去除。
RO106741描述了一种在下流式方法中，于固定床反应器中将糠醛氢化成糠醇的方法。特别使用拉尼铜作为催化剂。该出版物没有任何有关该催化剂的制备及其性能的信息。
JP-A-3 141 235公开了一种将丙酮氢化成异丙醇的方法，其中使用了拉尼镍催化剂。它描述了将拉尼镍催化剂与拉尼铜催化剂混合。但是它同时明确地声称，催化剂的加入量超过某一特定值时，生产率将降低。
可用于固定床法的拉尼催化剂一般这样制备：使用粘合剂和助剂来捏合铝/铜合金粉末，由该捏合组合物制成片剂或挤出物之类的模制品，煅烧该模制品，然后通过用碱金属氢氧化物进行处理来活化该煅烧模制品。这种制备拉尼催化剂的方法描述于，例如DE-A4345265、工业与工程化学综述(Ind.Eng.Chem.Res.)28(1989)1764-1767和DE-A4446907。通过该方法制备催化剂包括多个步骤。
本发明的一个目的是提供一种采用易于工业制造且具有高活性和选择性的催化剂来催化氢化羰基化合物的方法。
已经发现，该目的可通过采用块金形式的拉尼铜，将羰基化合物氢化成(例如)相应醇而实现，该拉尼铜具有超过按照已有技术所得拉尼铜催化剂的活性和选择性的高催化活性和高选择性。
因此，该目的已通过一种在拉尼铜催化剂的存在下，催化氢化羰基化合物或两种或多种羰基化合物的混合物的方法而实现，其中采用了块金形式的拉尼铜催化剂。
块金是指，该金属处于尺寸为0.5-10毫米的不规则几何形状颗粒形式。该拉尼铜块金通过使用碱金属氢氧化物来处理粗颗粒铜/铝合金，由粗颗粒铜/铝合金制成，其中没有了采用粘合剂和/或助剂来捏合铜/铝合金、将捏合组合物成型为模制品并煅烧该模制品的这些中间步骤。
用于本发明的块金尺寸可以是0.5-10毫米。它们优选为1-8毫米，尤其优选2-7毫米，特别是2-6毫米。
用于本发明的拉尼铜由铜/铝合金开始制备。铜/铝合金可通过本身已知的方式，例如通过DE-A2159736所述方法来制备。起始合金中铝与铜的重量比一般选择在30∶70-70∶30％重量，优选40∶60-60∶40％重量。
该拉尼铜催化剂通过用碱金属氢氧化物溶解出催化惰性组分(活化作用)，由铜/铝合金制成。优选的碱金属氢氧化物为氢氧化钠或氢氧化钾，特别优选氢氧化钠。一般使用碱金属氢氧化物的水溶液，优选氢氧化钠或氢氧化钾溶液，尤其优选氢氧化钠溶液，通常使用5-30％重量的碱金属氢氧化物水溶液。碱金属氢氧化物与铝的摩尔比一般选择在1∶1-4∶1，优选1.5∶1-2.5∶1。活化通常在25-95℃，优选45-90℃下进行。活化持续时间基本上取决于所需的最终铝含量，且一般为10-30小时，优选15-25小时。活化通过在此过程中测量所释放的氢气量而容易控制。活化步骤还可进行几次。
用于活化的起始原料通常是粗颗粒铜/铝合金。铜/铝合金颗粒的尺寸可对应于本发明所用的拉尼铜块金的尺寸。但也可在活化之后将颗粒降低到所需尺寸。
用于本发明的拉尼铜催化剂的铜含量为40-90％重量，优选50-80％重量，尤其优选60-70％重量。
用于本发明的拉尼铜催化剂的Langmuir比表面积为5-50米2/克，优选15-40米2/克，尤其优选20-40米2/克。Langmuir比表面积使用DIN 66 132法，通过氮气吸收来测定。
此外，按照本发明的拉尼铜催化剂的一个可变特性是其比铜表面积(S-Cu)。它由N2O消耗值计算，该消耗值是在受热催化剂样品中使用气态N2O氧化表面铜原子时测得的。
这可开始时通过用10毫巴H2，在240℃下处理4小时来进行。然后将样品上的压力降低到低于10-3毫巴，然后用30毫巴H2处理3小时，随后再将压力降低到低于10-3毫巴，然后用100毫巴H2处理3小时，再将压力降低到低于10-3毫巴，然后用200毫巴H2处理3小时，每种情况下的氢气处理都是在240℃下进行的。
在第二步中，将样品在266毫巴的压力下，在70℃下暴露于N2O小时，N2O在样品上分解；然后将样品上的压力降低到低于10-3毫巴，之后，测定催化剂由于在其表面上形成氧化铜而导致的重量增加。
拉尼铜催化剂的比Cu表面积为0.5-7米2/克，优选1-4米2/克。
通过水银孔率计测得的拉尼铜催化剂的孔体积为0.01-0.12毫升/克，优选0.03-0.08毫升/克。通过该方法测得的平均孔径为50-300纳米，优选60-100纳米。水银孔体积和孔径是通过DIN 66 133法测得的。
用于本发明方法的拉尼铜块金的表观密度一般为1.9-2.4克/毫升，优选1.9-2.1克/毫升。
按照本发明的方法可作为固定床反应(其中催化剂在固定床中)，或作为流化床反应(其中催化剂进行流化)来进行。优选使用固定床。氢化可在气相或液相中进行。氢化优选在液相中，例如在下流式或上流式方法中进行。
在采用下流式方法的本发明方法的一个优选实施方案中，将通过反应器之后的部分产物作为产物流连续取出，将其它部分的产物与包含羰基化合物的新鲜前体一起返回到反应器中。该方式以下称作再循环方式。
在下流式方法中，将包含待氢化羰基化合物的液体前体向下流到催化剂床上，该催化剂床位于反应器中，处于高压氢气下，并在该催化剂上形成液体薄膜。另一方面，在上流式方法中，将氢气通过填充有液体反应混合物的反应器中，这时将氢气作为上升气泡通过催化剂床。
在上流式方法中，按照本发明的方法可间歇或连续进行。该方法可这样连续进行：取出通过反应器之后的所有液体产物；或按照类似于上述的方式，仅取出部分产物，并将其它部分的产物与包含羰基化合物的新鲜前体一起返回到反应器中(再循环方式)。该方法优选连续进行，其中在前体一次(直接)通过反应器之后，取出所有的产物。
按照本发明的方法适用于将羰基化合物，如醛和酮氢化成相应醇，其中优选脂族和环脂族饱和和不饱和羰基化合物。在芳族羰基化合物的情况下，由于芳族核的氢化而非所需地形成副产物。羰基化合物可具有其它的官能团，如羟基或氨基。一般将不饱和羰基化合物氢化成相应的饱和醇。用于本发明的术语“羰基化合物”包括具有C＝O基团的所有化合物，其中包括羧酸及其衍生物。
按照本发明的方法优选用于氢化脂族醛、羟基醛、酮、酸、酯、酸酐、内酯和糖。例如，可以采用脂族醛或脂族羟基醛或其两种或多种的混合物作为羰基化合物。
优选的脂族醛为直链或支链的饱和和/或不饱和脂族C2-C30醛，它们例如可通过羰基合成法由具有内或端双键的直链或支链烯烃得到。
脂族醛的例子为：
丙醛、正丁醛、异丁醛、戊醛、2-甲基丁醛、3-甲基丁醛(异戊醛)、2，2-二甲基丙醛(新戊醛)、己醛、2-甲基戊醛、3-甲基戊醛、4-甲基戊醛、2-乙基丁醛、2，2-二甲基丁醛、3，3-二甲基丁醛、辛醛和癸醛。
除了所提及的短链醛之外，长链脂族醛也是特别合适的，它们例如可通过羰基合成法由直链α-烯烃得到。
特别优选烯醇化产物，如2-乙基己醛、2-甲基戊醛、2，4-二乙基辛醛或2，4-二甲基庚醛。
优选的羟基醛为C3-C12羟基醛，它们例如可通过醛醇反应由脂族和环脂族醛和酮与自身或甲醛而得到。其例子为3-羟基丙醛、二羟甲基乙醛、三羟甲基乙醛(季戊四醛)、3-羟基丁醛(丁间醇醛)、3-羟基-2-乙基己醛(丁醛醇)、3-羟基-2-甲基戊醛(丙醛醇)、2-羟甲基丙醛、2，2-二羟甲基丙醛、3-羟基-2-甲基丁醛、3-羟基戊醛、2-羟甲基丁醛、2，2-二羟甲基丁醛和羟基新戊醛。羟基新戊醛(HPA)和二羟甲基丁醛(DMB)是特别优选的。
优选的酮为丙酮、丁酮、2-戊酮、3-戊酮、2-己酮、3-己酮、环己酮、异佛尔酮、甲基·异丁基酮、亚异丙基丙酮、苯乙酮、苯基·乙基酮、二苯甲酮、亚苄基丙酮、二亚苄基丙酮、亚苄基苯乙酮、2，3-丁二酮、2，4-戊二酮、2，5-己二酮和甲基·乙烯基酮。
也可将羧酸及其衍生物(优选具有1-20个碳原子的)进行反应。尤其可以提及以下物质：
羧酸，如甲酸、乙酸、丙酸、丁酸、异丁酸、正戊酸、三甲基乙酸(新戊酸)、己酸、庚酸、辛酸、癸酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、丙烯酸、甲基丙烯酸、油酸、反油酸、亚油酸、亚麻酸、环己酸、苯甲酸、苯基乙酸、邻甲苯甲酸、间甲苯甲酸、对甲苯甲酸、邻氯苯甲酸、对氯苯甲酸、邻硝基苯甲酸、对硝基苯甲酸、水杨酸、对羟基苯甲酸、邻氨基苯甲酸、对氨基苯甲酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、马来酸、富马酸、1，4-环己烷二甲酸、邻苯二甲酸、间苯二甲酸和对苯二甲酸；
羰基卤化物，如上述羧酸的酰氯或酰溴，尤其是乙酰氯或乙酰溴、硬脂酰氯或溴以及苯甲酰氯或溴(尤其能进行脱卤化)；
羧酸酯，如上述羧酸的C1-C10烷基酯，尤其是甲酸甲酯、乙酸乙酯、丁酸丁酯、对苯二甲酸二甲酯、己二酸二甲酯、(甲基)丙烯酸甲酯、丁内酯、己内酯和聚羧酸酯，如聚丙烯酸聚甲基丙烯酸酯及其共聚物和聚酯，如聚(甲基丙烯酸甲酯)，在这些情况下尤其进行氢解反应，即将酯转化成相应的酸和醇；
羧酸酐，如上述羧酸的酸酐，尤其是乙酸酐、丙酸酐、苯甲酸酐和马来酸酐；
碳酰胺，如甲酰胺、乙酰胺、丙酰胺、硬脂酰胺和对苯二甲酰胺。
也可将羟基羧酸，如乳酸、苹果酸、酒石酸或柠檬酸，或氨基酸如甘氨酸、丙氨酸、脯氨酸或精氨酸进行反应。
按照本发明的方法尤其优选用于氢化醛和羟基醛。
待氢化羰基化合物可作为气体或液体单独或作为与氢化产物的混合物加料到氢化反应器中，而且该液体可以是未稀释的形式或与附加溶剂混合。特别合适的附加溶剂为水，醇如甲醇、乙醇和在反应条件下生成的醇。优选的溶剂为水、THF、NMP和酯如二甲酯和二乙酯、MTBE，水是特别优选的。
在上流和下流式方法中，氢化一般都在50-250℃，优选70-200℃，尤其优选100-140℃下，在15-250巴，优选20-200巴，尤其优选25-100巴的压力下进行。
通过本发明的方法可实现高转化率和选择性。所用的催化剂具有比已有技术催化剂高的活性。因此，可在明显较高的空间速率下进行氢化，而不会损失转化率和选择性。此外，该催化剂由于省去了成型和煅烧之类的步骤而易于制备。这使得按照本发明的方法特别经济。
以下通过实施例详细说明本发明。
实施例1：在下流式方法中将羟基新戊醛(HPA)氢化成新戊二醇(NPG)
起始溶液包含38％重量HPA和38％重量NPG在24％重量水中的混合物。在下流式方法和再循环方式中(再循环9.5升/小时)，在长50厘米、内径4.25厘米(反应器容积200毫升)的反应器中，在0.35升HPA/升催化剂×小时的空间速率下，在130℃、35巴下将该混合物氢化，其中所述反应器装有：
a)200毫升作为催化剂A的Al2O3承载铜催化剂，按照EP-A0044444所述制备的片剂形式(3×3毫米)，Cu含量为36％重量，表观密度为1090克/升，BET表面积为101米2/克，比Cu表面积为11.5米2/克，
或
b)200毫升作为催化剂B的SiO2承载铜催化剂，按照WO95/32171所述制备的珠粒形式(直径3毫米)，Cu含量为18％重量，表观密度为605克/升，BET表面积为212米2/克，比Cu表面积为9.8米2/克，
或
c)200毫升作为催化剂C的拉尼铜催化剂，按照DE-A4446907所述制备的片剂形式(3×3毫米)，Cu含量为72％重量，表观密度为2000克/升，Langmuir比表面积为24米2/克，比Cu表面积为2.6米2/克，Hg孔体积为0.06毫升/克，平均孔径(通过Hg孔率计测定)为84纳米
或
d)200毫升作为催化剂D(按照本发明)的块金(直径3毫米)形式拉尼铜，Cu含量为56％重量，表观密度为1950克/升，Langmuir比表面积为26米2/克，比Cu表面积为3.1米2/克，Hg孔体积为0.07毫升/克，平均孔径(通过Hg孔率计测定)为92纳米。
实施例2：在上流式方法中将2，2-二羟甲基丁醛(DMB)氢化成1，1，1-三羟甲基丙烷
起始溶液是45％重量的DMB水溶液。在上流式方法中，在长30厘米、内径2.5厘米、装有150毫升来自实施例1的催化剂B、C或D(按照本发明)的反应器中，在120℃、90巴下将该溶液氢化。在不同的空间速率：0.2、0.3、0.4和0.6千克DMB/升催化剂×小时下，将该溶液连续泵抽通过反应器。
表1汇总了这些结果。
结果清楚表明，在其它条件相同的情况下，使用催化剂D可实现最高的转化率和选择性。
表1
| 催化剂 | 前体 | 方法 | 空间速率千克/升催化剂×小时 | 转化率(得自GC％面积)％ | 选择性(得自GC％面积)％ |
| A | HPA | 下流式/再循环 | 0.35 | 86.8 | 89.1 |
| B | HPA | 下流式/再循环 | 0.35 | 94 | 92.5 |
| B | DMB | 上流式 | 0.2 | 99.44 | 78.91 |
| B | DMB | 上流式 | 0.3 | 90.84 | 75.28 |
| C | HPA | 下流式/再循环 | 0.35* | 95.2 | 93.3 |
| C | DMB | 上流式 | 0.2 | 100 | 89.97 |
| C | DMB | 上流式 | 0.4 | 97.65 | 87.34 |
| C | DMB | 上流式 | 0.6 | 88.79 | 74.52 |
| D | HPA | 下流式/再循环 | 0.35 | 96.8 | 94.2 |
| D | DMB | 上流式 | 0.2 | 100 | 91.17 |
| D | DMB | 上流式 | 0.4 | 100 | 90.7 |
| D | DMB | 上流式 | 0.6 | 95.45 | 87.3 |
*升HPA/千克催化剂×小时
Claims (10)
1.一种在拉尼铜催化剂的存在下催化氢化羰基化合物或两种或多种羰基化合物的混合物的方法，其中采用了块金形式的拉尼铜催化剂，并且所述块金是尺寸为0.5-10毫米的不规则几何形状的颗粒，其中所述拉尼铜催化剂具有以下性能：
-铜含量为40-90％重量
-Langmuir比表面积为5-50米2/克
-铜比表面积为0.5-7米2/克
-Hg孔体积为0.01-0.12毫升/克
-平均孔径为50-300纳米。
2.根据权利要求1所要求的方法，其中所述块金尺寸为2-7毫米。
3.根据权利要求1所要求的方法，其中所述催化氢化是在下流式方法中作为固定床反应来进行的。
4.根据权利要求1所要求的方法，其中所述催化氢化是在上流式方法中作为固定床反应来进行的。
5.根据权利要求3或4所要求的方法，其中所述方法还在再循环方式下进行。
6.根据权利要求3或4所要求的方法，其中所述氢化是在70-200℃下、在20-200巴的压力下进行的。
7.根据权利要求1所要求的方法，其中采用了脂族醛或脂族羟基醛或其两种或多种的混合物作为羰基化合物。
8.根据权利要求7所要求的方法，其中采用了羟基新戊醛或二羟甲基丁醛作为羰基化合物。
9.根据权利要求1所要求的方法，其中水作为溶剂存在。
10.根据权利要求7所要求的方法，其中水作为溶剂存在。
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| US6455742B1 (en) | 1999-09-02 | 2002-09-24 | Wisconsin Alumni Research Foundation | Method for catalytically reducing carboxylic acid groups to hydroxyl groups in hydroxycarboxylic acids |
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| US7329786B2 (en) * | 2001-09-28 | 2008-02-12 | Great Lakes Chemical Corporation | Processes for producing CF3CFHCF3 |
| US7223351B2 (en) * | 2003-04-17 | 2007-05-29 | Great Lakes Chemical Corporation | Fire extinguishing mixtures, methods and systems |
| US20050038302A1 (en) * | 2003-08-13 | 2005-02-17 | Hedrick Vicki E. | Systems and methods for producing fluorocarbons |
| CA2496839A1 (en) | 2004-07-19 | 2006-01-19 | Woodland Chemical Systems Inc. | Process for producing ethanol from synthesis gas rich in carbon monoxide |
| DE102005049135A1 (de) * | 2005-10-14 | 2007-04-19 | Basf Ag | Verfahren zur Hydrierung von Carbonylverbindungen |
| CN100348292C (zh) * | 2005-12-08 | 2007-11-14 | 哈尔滨工业大学 | 一种从水中获取空气的装置及其方法 |
| EA013194B1 (ru) * | 2006-04-05 | 2010-02-26 | Вудлэнд Байофьюэлс Инк. | Способ получения этанола |
| AR072446A1 (es) * | 2008-03-02 | 2010-09-01 | Dow Global Technologies Inc | Proceso de hidrogenacion mejorado |
| WO2010115738A1 (de) | 2009-04-07 | 2010-10-14 | Basf Se | Verfahren zur herstellung von 1,6-hexandiol |
| WO2010115798A2 (de) | 2009-04-07 | 2010-10-14 | Basf Se | Verfahren zur herstellung von 1,6-hexandiol und caprolacton |
| EP2559679A3 (de) | 2009-04-08 | 2013-05-22 | Basf Se | Verfahren zur Herstellung von 1,6-Hexandiol durch Hydrierung von Oligo- und Polyestern |
| CN104513130B (zh) * | 2013-09-30 | 2016-04-27 | 中国石油化工股份有限公司 | 一种醛选择加氢制备醇的方法 |
| CN104945225B (zh) * | 2014-03-27 | 2017-02-15 | 中国石油化工股份有限公司 | 一种癸烯醛加氢制备醇的方法 |
| CN105481647B (zh) * | 2014-09-16 | 2017-07-28 | 中国石油化工股份有限公司 | 一种醋酸酯加氢制备乙醇的方法 |
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| CN106543115B (zh) * | 2016-10-30 | 2018-09-14 | 中南民族大学 | 一种利用氢转移反应催化糠醛制备糠醇的方法 |
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